Lubricant



Patented Nov. 4:1941

FICE

LUBRICANT William A. Whittier, Kenilworth,

The Pure Oil tion of Ohio Company,

111., assignor to Chicago, 111., a corpora- No Drawing. ApplicationDecember 18, 1937,

Serial No. 180,487

19 Claims.

This invention relates to lubricants and to the method of preparing andof using the same, and is more particularly concerned with lubricantshaving extreme pressure characteristics.

' It is well known that mineral lubricating oils can be improved byadding thereto halogenated aromatic hydrocarbons and compounds, in whichhydrogen in the aromatic nucleus is substituted by chlorine. Halogenatedaliphatic hydrocarbons ;and compounds in general have been found to -beunsatisfactory because such compounds hydrolyze readily in contact withwater forming acid which corrodes the metal surfaces.

I have discovered that where halogen is linked to aliphatic carbon,which is protected on both ends byv a non-acidic, stable aromatic orother' carbocyclic nuclei, the resulting compounds are not only notcorrosive but are more active than the halogenated aromatics. Suchcompounds have the ability to impart to mineral lubricating oils,increased oiliness, film strength, and extreme pressure characteristics.

The compounds which I have discovered to be suitable arest h se of thetype in which R and R are non-acidic, stable aromatic orothercarbocyclic nuclei, either the same or difierent, C represents analiphatic radical either saturated or unsaturated having any number (12)of carbon atoms in excess of one carbon, and Ha represents a halogenunited to one or more aliphatic straight chain carbon atoms which arelinked between the carbocyclic nuclei.

Examples of compounds which are suitable for use are symmetricaldiphenyl ethane (dibenzyl) symmetrical diphenyl ethylene, symmetricaldiphenyl acetylene, symmetrical diphenyl butane, symmetrical diphenylpropane, symmetrical diphenyl butadiene, 1 phenyl 3-naphthyl propane,l-naphthyl 4-phenyl butene-2, symmetrical dinaphthyl propane, l-xenyl4-phenyl butane, 1- naphthyl 3-xenyl propane, 1-4 dixenyl butane, 1-4dltolyl butadiene, symmetrical diphenyl diethyl ether, l-phenylG-naphthyl dipropylether, and symmetrical diphenyl ethylene ether, inwhich halogen is united to one or more aliphatic carbon atoms linkedbetween the aromatic nuclei. The halogen may be added directly to thethe carbon by direct carbon in those compounds which are unsaturated ormay replace the hydrogen in those com- Pounds which are saturated. Inthe case'of unsaturated compounds, halogen may be linked to blended withaddition, and by substitution of the hydrogen. Generally speaking, thegreater the number of chlorine atoms linked to the carbon, the greaterthe activity of the compound and the greater is its efl'ectiveness.

To illustrate graphically the nature of the compounds with which thisinvention is concerned,

(Sym. diphenyl ethylene) I (Dichlor dibenzyl) By using 3 molecules canbe replaced and 2 chlorine atoms attached to each carbon therebyobtaining tetrachlor dibenzyl. This type of reaction is relativelysimple and well understood.

The halogenated compounds may be used in connection with straightmineral lubricating oils or in connection with oils which have beenblended with other reagents to improve the lubricati'ng characteristicsthereof. For example,

I have found that when small quantities of halogenated compounds of thenature of those above described are incorporated in a blend of minegallubricating oil with a sulfurized and phosphorized fatty the applicationthe extreme pressure characteristics of such lubricants can bematerially improved. A number of tests have been made on straightlubricants halogenated compounds of the nature of those above set forthand on'lubricants blended with sulfurized and phosphorized base togetherwith halogenated compounds, and the results'given in the table tests thestraight mineral oil used was a blend in the proportions of 1:1 of twomineral lubricating oils of the following characteristics:

Table I Oil No. 1 ohm. z

A. .1. gravit 21-.5-23 I Flash, su i aig Fire, F 385405 5904500 Vls. at13 98-102 1150-2100 Vis. at 21 43-45 -165 Pour point, -20 25 ColorN. A2-3v 8 In those tests in which an oil blended withsulfuIized-phosphorized base was used, the lubriof chlorine the hydrogenoil base "suchas that disclosed-in of Whittier et al., Ser. No. 55,200,

below. In these cating oil, before addition of the base, had thefollowing characteristics:

Table II A. P. I. gravity-- 18-20 Flash, F 380-400 Fire, "F 430-450 Vis.at 130". 1*. (Say. Univ.) 460-500 Vis. at 210 F. (Say Univ.) 90-95 Pourpoint,

This oil was blended with sulfurized-phosphorized base in, theproportion of 82% of oil to 18% of base. 1

The sulfurized-phosphorized base was made in kettle. when thistemperature had been reached, 44 pounds of phosphorous sesqui-sulfidewas added slowly over a period of hour of continuous agitation. 'Thesteam was again turned 0 on at such times as was necessary to maintainthe temperature at 220 to 230 '1. After the addition of phosphorous,agitation was continued for a period of approximately 5 hours while thetemperature was maintained at 220 to 230 .F. At the end of this periodthe contents of the kettle were immediately cooled to 130 F. bycirculation through the exteriorly located cooling coils and pumped tostorage.

The following is a table of the results obtained:

Table III Halogenated compound added 13mg Oil used tor blend Sui-plies.base blend Plain mineral oil lubricant... Trichlor dibenzyl. 5

Hera chlor sym. diphenyl nonane Octa chlor sym. dipiienyl nonadecane.-.

Sul-phos. base bland do Plain mineral oil lubricant. Sui-3110s. baseblend.

the following manner: A homogeneous mixture of 5'70 pounds of Gulf Coastpale oil having a Saybolt Universal viscosity of 200 seconds and a pourpoint of to F. and pounds of sulfur chloride was prepared in a coldstate. This mixture was added to 9,581 pounds of prime lard oilcontained in an enclosed steam jacketed kettle. The mixture was heatedto 275 F. while beingvigorously agitated. At this point the steam wasshut oil and 814 pounds of flowers of sulfur were sifted into thecontents of the kettle over a period of approximately 2 hours. Thecontents of the kettle were vigorously agitated during this entireperiod. At the end of the 2-hour period the temperature had dropped to265 F. The steam was again turned on and the contents or thekettleheated to approximately 300 F. when the steam was turned oflf.Agitation was continued for a period of approximately 7 hours after theaddition of the sulfur. During this period the temperature rose from 300to 344 F. during the first 3 hours indicating that an exothermicreaction was taking place. Thetemperature during the 'l -hour period-wasnot permitted to drop below 320 to 330 F. and it was found that it wasunnecessary to use any further heat to maintain this temperature afterthe mixture had been initially heated to 300 F.

The sulfurized material .was then cooled to a temperature of 220 to 230F. by circulating the material through cooling coils The tests were madeon the SAE extreme pressure testing machine which is used in theautomotive industry to determine the suitability of extreme pressurelubricants. The maximum load that can be measured on the machine withsafety is between 550 and 570 pounds.

As shown above, the sulfurized-phosphorized lubricant, without additionof the halogen compound, withstood a load of only 90 pounds. Acomparative test of the sulfurized-phosphorized base lubricant and thesame lubricant to which had been added 5% of trichlor dibenzyl was madeon the Faville-Levalley machine and the former withstood a load --ofonly 2000 pounds whereas the later withstood a load of 4200 pounds. When8 to 10% of trichlor debenzyl was added, the material withstood a loadof 4500 pounds on the Faville-Levalley machine, which is the maximum forthat machine. The E. P. characteristics of the sulfurized-phosphorizedbase lubricant, as determined by the "fimken machine,

is not appreciably altered by addition of the halogen compound. Theaddition of the halogenated compound, while greatly increasing the filmstrength and E. P. characteristics of the lubricant, had no detrimentaleffect thereon. Corrosion tests made in the presence of water indicatethat as much as 10% of the halogenated compound may be introduced intothe lubricant without rendering it corrosive.

and back to the The sulfurized-phosphorized base lubricant to which 7%of trichlor dibenzyl had been added, was placed in the difierential of anew automobile and the gears were checked after 1015 miles and at theend of 3638 miles. The original backlash in the gears was .006 inch. Atthe end of 1015 miles, the backlash was .007 inch, and the back-.

lash at the end of 3638 miles was also .007 inch,

- thus indicating that the rear end ironed itself motor oil, the amountadded may range from a 6 fraction of 1% to approximately 5%. The upperlimit of 10% has been fixed only because with the methods of testing nowavailable, it has been found that maximum results can be obtained byadding this amount. There is no reason, however, why quantities inexcess of 10% may not be used.

Although I have tried chlorinated diphenyl methane in which the chlorineis linked to the carbon in the methyl radical, I have found thiscompound is unstable and therefore unsuitable for use.

Instead of adding the halogenated compound directly to the oil, it maybe separately fed into the particular mechanism to be lubricated andmixed in situ with the lubricating oil.

What I claim is:

7. A lubricant comprising mineral lubricating oil and chlorinated 1-4dixenyl butane in which chlorine is united to carbon in the aliphaticchain.

8. A lubricant comprising a major portion of mineral oil and a minorportion of a halogenated compound of the type RF-CnR' in which R and Rare non-acidic stable carbocyclic radicals, C is a straight aliphaticchain having any number (11) of carbon atoms in excess of one, andhalogen is linked to carbon in the aliphatic chain.

9. A lubricant in accordance with claim 8 containing a minor proportionof sulfurized and phosphorized fatty body,

10. A lubricant in accordance with claim 8 in I which R and R are arylradicals.

1. A lubricant comprising a mineral lubricating oil and a compound ofthe type @OWOO in which the hydrogen in the benzene rings is halogensubstituted or unsubstituted, C is an aliphatic radical having anynumber (n) of carbon atoms in excess of one, and a halogen is united toaliphatic carbon.

2. A lubricant in accordance with claim 1 in which C is an aliphatichydrocarbon radical.

3. A lubricant comprising mineral lubricating 0 11. A lubricantcomprising a major portion of mineral lubricating oil and a minorportion of halogenated dibenzyl.

12. A lubricant comprising a major portion of mineral lubricating oiland a minor portion of chlorinated dibenzyl.

13. A lubricant comprising a major portion of mineral lubricating oiland a minor portion of tetrachlor dibenzyl.

14. A lubricant comprising a major portion of mineral lubricating oiland .a minor portion of halogenated compound of the type where R and Rrepresent non-acidic, stable carbocyclic radicals and CH represents anyaliphatic hydrocarbon radical having halogen united to the carbon insaid last-mentioned radical.

15. A lubricant in accordance with claim 14 in which R and R arenon-acidic, stable aromatic nuclei.

16. A lubricant comprising a major portion of mineral lubricating oiland a minor portion of a a compound of the type Rr-C(n)R in which R andR are non-acidic, stable aryl radicals, C is an aliphatic hydrocarbonchain having any number (n) of carbon atoms in excess of one and ahalogen is linked to carbon in the aliphatic chain.

17. A lubricant in accordance with claim 14 in which R and R' arenon-acidic, stable aromatic nuclei and which lubricant containssulfurized and phosphorized fatty oil.

18. A lubricant comprising mineral lubricating oil and halogenatedsymmetrical diphenyl diethyl ether in which halogen is united to carbonin the aliphatic chain.

19. A lubricant in accordance with claim 18 in which the halogen ischlorine.

WILLIAM A. WHITTIER.

